Rapid aberration measurement with pixelated detectors.

Aberration-corrected microscopy in a scanning transmission electron microscope requires the fast and accurate measurement of lens aberrations to align or 'tune' the corrector. Here, we demonstrate a method to measure aberrations based on acquiring a 4D data set on a pixelated detector. Our method is compared to existing procedures and the choice of experimental parameters is examined. The accuracy is similar to existing methods, but in principle this procedure can be performed in a few seconds and extended to arbitrary order. This method allows rapid measurement of aberrations and represents a step towards more automated electron microscopy.

Gold nanotriangles decorated with superparamagnetic iron oxide nanoparticles: a compositional and microstructural study.

The combination of iron oxide and gold in a single nanoparticle results in both magnetic and plasmonic properties that can stimulate novel applications in bio-sensing, medical imaging, or therapeutics. Microwave assisted heating allows the fabrication of multi-component, multi-functional nanostructures by promoting selective heating at desired sites. Recently, we reported a microwave-assisted polyol route yielding gold nanotriangles decorated with iron oxide nanoparticles. Here, we present an in-depth microstructural and compositional characterization of the system using scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). A method to remove the iron oxide nanoparticles from the gold nanocrystals and some insights on crystal nucleation and growth mechanisms are also provided.

Probing plasmons in three dimensions by combining complementary spectroscopies in a scanning transmission electron microscope.

The nanoscale optical response of surface plasmons in three-dimensional metallic nanostructures plays an important role in many nanotechnology applications, where precise spatial and spectral characteristics of plasmonic elements control device performance. Electron energy loss spectroscopy (EELS) and cathodoluminescence (CL) within a scanning transmission electron microscope have proven to be valuable tools for studying plasmonics at the nanoscale. Each technique has been used separately, producing three-dimensional reconstructions through tomography, often aided by simulations for complete characterization. Here we demonstrate that the complementary nature of the two techniques, namely that EELS probes beam-induced electronic excitations while CL probes radiative decay, allows us to directly obtain a spatially- and spectrally-resolved picture of the plasmonic characteristics of nanostructures in three dimensions. The approach enables nanoparticle-by-nanoparticle plasmonic analysis in three dimensions to aid in the design of diverse nanoplasmonic applications.

Characterizing the two- and three-dimensional resolution of an improved aberration-corrected STEM.

The successful development of third-order aberration correctors in transmission electron microscopy has seen aberration-corrected electron microscopes evolve from specialist projects, custom built at a small number of sites to common instruments in many modern laboratories. Here we describe some initial results illustrating the two- and three-dimensional (3D) performance of an aberration-corrected scanning transmission electron microscope with a prototype improved aberration corrector designed to also minimize fifth-order aberrations and a new, higher brightness gun. We show that atomic columns separated by 0.63 A can be resolved and demonstrate detection of single dopant atoms with 3D sensitivity.

Big Data Analytics for Scanning Transmission Electron Microscopy Ptychography.

Electron microscopy is undergoing a transition; from the model of producing only a few micrographs, through the current state where many images and spectra can be digitally recorded, to a new mode where very large volumes of data (movies, ptychographic and multi-dimensional series) can be rapidly obtained. Here, we discuss the application of so-called "big-data" methods to high dimensional microscopy data, using unsupervised multivariate statistical techniques, in order to explore salient image features in a specific example of BiFeO3 domains. Remarkably, k-means clustering reveals domain differentiation despite the fact that the algorithm is purely statistical in nature and does not require any prior information regarding the material, any coexisting phases, or any differentiating structures. While this is a somewhat trivial case, this example signifies the extraction of useful physical and structural information without any prior bias regarding the sample or the instrumental modality. Further interpretation of these types of results may still require human intervention. However, the open nature of this algorithm and its wide availability, enable broad collaborations and exploratory work necessary to enable efficient data analysis in electron microscopy.

Localization in elastic and inelastic scattering.

The degree of information localization in elastic and inelastic scattering is examined in the context of imaging zone axis crystals in the aberration corrected STEM. We show that detector geometry is a critical factor in determining the localization, and compare a number of different geometries. Experimental core loss line traces demonstrate strong EELS localization at the titanium L-edge, even in the presence of dynamical elastic scattering.

Ubiquitous long-range antiferromagnetic coupling across the interface between superconducting and ferromagnetic oxides.

The so-called proximity effect is the manifestation, across an interface, of the systematic competition between magnetic order and superconductivity. This phenomenon has been well documented and understood for conventional superconductors coupled with metallic ferromagnets; however it is still less known for oxide materials, where much higher critical temperatures are offered by copper oxide-based superconductors. Here we show that, even in the absence of direct Cu-O-Mn covalent bonding, the interfacial CuO2 planes of superconducting La(1.85)Sr(0.15)CuO(4) thin films develop weak ferromagnetism associated to the charge transfer of spin-polarised electrons from the La(0.66)Sr(0.33)MnO(3) ferromagnet. Theoretical modelling confirms that this effect is general to all cuprate/manganite heterostructures and the presence of direct bonding only affects the strength of the coupling. The Dzyaloshinskii-Moriya interaction, also at the origin of the weak ferromagnetism of bulk cuprates, propagates the magnetisation from the interface CuO2 planes into the superconductor, eventually depressing its critical temperature.

Aberration measurement using the Ronchigram contrast transfer function.

The bright field contrast transfer function is one of the most useful concepts in conventional transmission electron microscopy. However, the electron Ronchigram contrast transfer function, as derived by Cowley, is inherently more complicated since it is not isoplanatic. Here, we derive a local contrast transfer function for small patches in a Ronchigram and demonstrate its utility for the direct measurement of aberrations from single Ronchigrams of an amorphous film. We describe the measurement of aberrations from both simulated and experimental images and elucidate the effects due to higher-order aberrations, separating those arising from the pre- and post-sample optics, and partial coherence.

Spectroscopic imaging of electron energy loss spectra using ab initio data and function field visualization.

We have devised a technique for spectral imaging using accurate ab initio electron energy loss near edge structure (ELNES) data and function field visualization. The technique is initially applied to a planar defect model in Si with different ring structures and no broken bonds where experimental probes are severely limited. The same model with B doping is also considered. It is shown that specific deviations in different energy ranges of the ELNES spectra are correlated with different structural components of the models.

Aberration-corrected scanning transmission electron microscopy: from atomic imaging and analysis to solving energy problems.

The new possibilities of aberration-corrected scanning transmission electron microscopy (STEM) extend far beyond the factor of 2 or more in lateral resolution that was the original motivation. The smaller probe also gives enhanced single atom sensitivity, both for imaging and for spectroscopy, enabling light elements to be detected in a Z-contrast image and giving much improved phase contrast imaging using the bright field detector with pixel-by-pixel correlation with the Z-contrast image. Furthermore, the increased probe-forming aperture brings significant depth sensitivity and the possibility of optical sectioning to extract information in three dimensions. This paper reviews these recent advances with reference to several applications of relevance to energy, the origin of the low-temperature catalytic activity of nanophase Au, the nucleation and growth of semiconducting nanowires, and the origin of the eight orders of magnitude increased ionic conductivity in oxide superlattices. Possible future directions of aberration-corrected STEM for solving energy problems are outlined.

Detection of single atoms and buried defects in three dimensions by aberration-corrected electron microscope with 0.5-A information limit.

The ability of electron microscopes to analyze all the atoms in individual nanostructures is limited by lens aberrations. However, recent advances in aberration-correcting electron optics have led to greatly enhanced instrument performance and new techniques of electron microscopy. The development of an ultrastable electron microscope with aberration-correcting optics and a monochromated high-brightness source has significantly improved instrument resolution and contrast. In the present work, we report information transfer beyond 50 pm and show images of single gold atoms with a signal-to-noise ratio as large as 10. The instrument's new capabilities were exploited to detect a buried Sigma3 {112} grain boundary and observe the dynamic arrangements of single atoms and atom pairs with sub-angstrom resolution. These results mark an important step toward meeting the challenge of determining the three-dimensional atomic-scale structure of nanomaterials.

Progress in aberration-corrected scanning transmission electron microscopy.

A new corrector of spherical aberration (C(S)) for a dedicated scanning transmission electron microscope (STEM) is described and its results are presented. The corrector uses strong octupoles and increases C(C) by only 0.2 mm relative to the uncorrected microscope. Its overall stability is greatly improved compared to our previous design. It has achieved a point-to-point resolution of 1.23 A in high-angle annular dark field images at 100 kV. It has also increased the current available in a 1.3 A-sized probe by about a factor of ten compared to existing STEMs. Its operation is greatly assisted by newly developed autotuning software which measures all the aberration coefficients up to fifth order in less than one minute. We conclude by discussing the present limits of aberration-corrected STEM, and likely future developments.

Atomic-resolution electron energy loss spectroscopy imaging in aberration corrected scanning transmission electron microscopy.

The "delocalization" of inelastic scattering is an important issue for the ultimate spatial resolution of innershell spectroscopy in the electron microscope. It is demonstrated in a nonlocal model for electron energy loss spectroscopy (EELS) that delocalization of scanning transmission electron microscopy (STEM) images for single, isolated atoms is primarily determined by the width of the probe, even for light atoms. We present experimental data and theoretical simulations for Ti L-shell EELS in a [100] SrTiO3 crystal showing that, in this case, delocalization is not significantly increased by dynamical propagation. Issues relating to the use of aberration correctors in the STEM geometry are discussed.

Direct sub-angstrom imaging of a crystal lattice.

Despite the use of electrons with wavelengths of just a few picometers, spatial resolution in a transmission electron microscope (TEM) has been limited by spherical aberration to typically around 0.15 nanometer. Individual atomic columns in a crystalline lattice can therefore only be imaged for a few low-order orientations, limiting the range of defects that can be imaged at atomic resolution. The recent development of spherical aberration correctors for transmission electron microscopy allows this limit to be overcome. We present direct images from an aberration-corrected scanning TEM that resolve a lattice in which the atomic columns are separated by less than 0.1 nanometer.

Spectroscopic imaging of single atoms within a bulk solid.

The ability to localize, identify, and measure the electronic environment of individual atoms will provide fundamental insights into many issues in materials science, physics, and nanotechnology. We demonstrate, using an aberration-corrected scanning transmission electron microscope, the spectroscopic imaging of single La atoms inside CaTiO3. Dynamical simulations confirm that the spectroscopic information is spatially confined around the scattering atom. Furthermore, we show how the depth of the atom within the crystal may be estimated.